Configurational analysis of cubebins and bicubebin from Aristolochia lagesiana and Aristolochia pubescens

(8S,8'R,9S)-, (8R,8'R,9R)-, and (8R,8',R,9S)-cubebins, together with (8R,8'R,8R,8'''R,9R,9S)-bicubebin, were isolated from Aristolochia lagesiana and Aristolochia pubescens. Their structures were determined by spectroscopic methods, including H-1 and C-13 NMR spectroscopy at low temperatures, and by chemical transformations. (c) 2006 Elsevier Ltd. All rights reserved.

Nickel(II) complexes of whole set of the simple ethylenediaminetetracarboxylate ligands:DFT study of complexes invoking molecular orbital and configurational analysis

The whole set of the nickel(II) complexes with no derivatized edta-type hexadentate ligands has been investigated from their structural and electronic properties. Two more complexes have been prepared in order to complete the whole set: trans(O5)-[Ni(ED3AP)]2- and trans(O5O6)-[Ni(EDA3P)]2- complexes. trans(O5) geometry has been verified crystallographically and trans(O5O6) geometry of the second complex has been predicted by the DFT theory and spectral analysis. Mutual dependance has been established between: the number of the five-membered carboxylate rings, octahedral/tetrahedral deviation of metal-ligand/nitrogen-neighbour-atom angles and charge-transfer energies (CTE) calculated by the Morokuma’s energetic decomposition analysis; energy of the absorption bands and HOMO–LUMO gap.

Copper(II) complexes with unsymmetrical pentadentate ed3a-type diamino-tricarboxylate ligands. Crystal structures, configurational analysis and DFT study of complexes

The O–O–N–N–O-type pentadentate ligands H3ed3a, H3pd3a and H3pd3p (H3ed3a stands ethylenediamine-N,N,N′-triacetic acid; H3pd3a stands 1,3-propanediamine-N,N,N′-triacetic acid and H3pd3p stands 1,3-propanediamine-N,N,N′-tri-3-propionic acid) and the corresponding novel octahedral or square-planar/trigonal-bipyramidal copper(II) complexes have been prepared and characterized. H3ed3a, H3pd3a and H3pd3p ligands coordinate to copper(II) ion via five donor atoms (three deprotonated carboxylate atoms and two amine nitrogens) affording octahedral in case of ed3a3− and intermediate square-pyramidal/trigonal-bipyramidal structure in case of pd3a3− and pd3p3−. A six coordinate, octahedral geometry has been established crystallographically for the [Mg(H2O)6][Cu(ed3a)(H2O)]2 · 2H2O complex and five coordinate square-pyramidal for the [Mg(H2O)5Cu(pd3a)][Cu(pd3a)] · 2H2O. Structural data correlating similar chelate Cu(II) complexes have been used for the better understanding the pathway: octahedral → square-pyramidal ↔ trigonal- bipyramid geometry. An extensive configuration analysis is discussed in relation to information obtained for similar complexes. The infra-red and electronic absorption spectra of the complexes are discussed in comparison with related complexes of known geometries. Molecular mechanics and density functional theory (DFT) programs have been used to model the most stable geometric isomer yielding, at the same time, significant structural data. The results from density functional studies have been compared with X-ray data.

Measurement and Applications of Long-Range Heteronuclear Scalar Couplings: Recent Experimental and Theoretical Developments

The use of long-range heteronuclear couplings, in association with 1H1H scalar couplings and NOE restraints, has acquired growing importance for the determination of the relative stereochemistry, and structural and conformational information of organic and biological molecules. However, the routine use of such couplings is hindered by the inherent difficulties in their measurement. Prior to the advancement in experimental techniques, both long-range homo- and heteronuclear scalar couplings were not easily accessible, especially for very large molecules. The development of a large number of multidimensional NMR experimental methodologies has alleviated the complications associated with the measurement of couplings of smaller strengths. Subsequent application of these methods and the utilization of determined J-couplings for structure calculations have revolutionized this area of research. Problems in organic, inorganic and biophysical chemistry have also been solved by utilizing the short- and long-range heteronuclear couplings. In this minireview, we discuss the advantages and limitations of a number of experimental techniques reported in recent times for the measurement of long-range heteronuclear couplings and a few selected applications of such couplings. This includes the study of medium- to larger-sized molecules in a variety of applications, especially in the study of hydrogen bonding in biological systems. The utilization of these couplings in conjunction with theoretical calculations to arrive at conclusions on the hyperconjugation, configurational analysis and the effect of the electronegativity of the substituents is also discussed.

Influence du financement sur la performance des systèmes de soins

La thèse a pour objectif d’étudier l’influence du financement des soins de santé sur la performance des systèmes de soins compte tenu des caractéristiques organisationnelles sanitaires des systèmes. Elle s’articule autour des trois objectifs suivants : 1) caractériser le financement des soins de santé à travers les différents modèles émergeant des pays à revenu élevé ; 2) apprécier la performance des systèmes de soins en établissant les divers profils apparaissant dans ces mêmes pays ; 3) examiner le lien entre le financement et la performance en tenant compte du pouvoir modérateur du contexte organisationnel des soins. Inspirée du processus de circulation de l’argent dans le système de soins, l’approche a d’abord consisté à classer les pays étudiés – par une analyse configurationnelle opérationnalisée par les analyses de correspondance multiples (ACM) et de classification hiérarchique ascendante (CHA) – dans des modèles types, chacun représentant une configuration particulière de processus de financement des soins de santé (article 1). Appliquée aux données recueillies auprès des 27 pays de l’OCDE à revenu élevé via les rapports Health Care in Transition des systèmes de santé des pays produits par le bureau Européen de l’OMS, la banque de données Eco-Santé OCDE 2007 et les statistiques de l’OMS 2008, les analyses ont révélé cinq modèles de financement. Ils se distinguent selon les fonctions de collecte de l’argent dans le système (prélèvement), de mise en commun de l’argent collecté (stockage), de la répartition de l’argent collecté et stocké (allocation) et du processus de paiement des professionnels et des établissements de santé (paiement). Les modèles ainsi développés, qui vont au-delà du processus unique de collecte de l’argent, donnent un portrait plus complet du processus de financement des soins de santé. Ils permettent ainsi une compréhension de la cohérence interne existant entre les fonctions du financement lors d’un éventuel changement de mode de financement dans un pays. Dans un deuxième temps, nous appuyant sur une conception multidimensionnelle de la performance des systèmes, nous avons classé les pays : premièrement, selon leur niveau en termes de ressources mobilisées, de services produits et de résultats de santé atteints (définissant la performance absolue) ; deuxièmement, selon les efforts qu’ils fournissent pour atteindre un niveau élevé de résultats de santé proportionnellement aux ressources mobilisées et aux services produits en termes d’efficience, d’efficacité et de productivité (définissant ainsi la performance relative) ; et troisièmement, selon les profils types de performance globale émergeant en tenant compte simultanément des niveaux de performance absolue et relative (article 2). Les analyses effectuées sur les données collectées auprès des mêmes 27 pays précédents ont dégagé quatre profils de performance qui se différencient selon leur niveau de performance multidimensionnelle et globale. Les résultats ainsi obtenus permettent d’effectuer une comparaison entre les niveaux globaux de performance des systèmes de soins. Pour terminer, afin de répondre à la question de savoir quel mode – ou quels modes – de financement générerait de meilleurs résultats de performance, et ce, dans quel contexte organisationnel de soins, une analyse plus fine des relations entre le financement et la performance (tous définis comme précédemment) compte tenu des caractéristiques organisationnelles sanitaires a été réalisée (article 3). Les résultats montrent qu’il n’existe presque aucune relation directe entre le financement et la performance. Toutefois, lorsque le financement interagit avec le contexte organisationnel sanitaire pour appréhender le niveau de performance des systèmes, des relations pertinentes et révélatrices apparaissent. Ainsi, certains modes de financement semblent plus attrayants que d’autres en termes de performance dans des contextes organisationnels sanitaires différents. Les résultats permettent ainsi à tous les acteurs du système de comprendre qu’il n’existe qu’une influence indirecte du financement de la santé sur la performance des systèmes de soins due à l’interaction du financement avec le contexte organisationnel sanitaire. L’une des originalités de cette thèse tient au fait que très peu de travaux ont tenté d’opérationnaliser de façon multidimensionnelle les concepts de financement et de performance avant d’analyser les associations susceptibles d’exister entre eux. En outre, alors que la pertinence de la prise en compte des caractéristiques du contexte organisationnel dans la mise en place des réformes des systèmes de soins est au coeur des préoccupations, ce travail est l’un des premiers à analyser l’influence de l’interaction entre le financement et le contexte organisationnel sanitaire sur la performance des systèmes de soins.

Gestions politiques de l'intégration des immigrants et des minorités etnoculturelles à Montréàl et à Laval (1960-2008)

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

What Counts Versus What Can Be Counted : The Complex Interplay of Market Orientation and Marketing Performance Measurement

Market orientation (MO) and marketing performance measurement (MPM) are two of the most widespread strategic marketing concepts among practitioners. However, some have questioned the benefits of extensive investments in MO and MPM. More importantly, little is known about which combinations of MO and MPM are optimal in ensuring high business performance. To address this research gap, the authors analyze a unique data set of 628 firms with a novel method of configurational analysis: fuzzy-set qualitative comparative analysis. In line with prior research, the authors find that MO is an important determinant of business performance. However, to reap its benefits, managers need to complement it with appropriate MPM, the level and focus of which vary across firms. For example, whereas large firms and market leaders generally benefit from comprehensive MPM, small firms may benefit from measuring marketing performance only selectively or by focusing on particular dimensions of marketing performance. The study also finds that many of the highest-performing firms do not follow any of the particular best practices identified.

KM governance:the mechanisms for guiding and controlling KM program

Purpose: To establish and sustain their KM programs organizations need to establish mechanisms to ensure their governance. KM programs require business integration, senior management involvement and decision making authority. The present research investigates the KM governance mechanisms organizations use to guide and control their KM programs. The research seeks to contribute to a better understanding of the governance of KM and to support organizations in the development of their KM programs. Methodology: The study employs multiple case research methodology to analyze the KM governance arrangements of twelve international organizations and identify patterns in their governance configurations. Findings: The analysis identifies a range of structural, process and relational mechanisms that are critical for governing an organizational KM program. Different patterns among the KM governance mechanisms are identified which lead to the development of generic KM governance typologies. Research implications: The development of the KM governance framework allows future research to systematically investigate the KM governance phenomenon. As the present study is based on a configurational analysis future research should particularly target the performance implications of different KM governance configurations. Practical implications: The research provides insights into the diversity of KM governance mechanisms and their impact on a KM program. The KM governance framework can assist managers in reviewing their present and prospective KM programs and thereby support benchmarking or re-organization efforts. Originality: Building on prior research that has focused on individual KM governance aspects, the present study adopts a comprehensive perspective integrating structural, process and relational governance mechanisms.

What counts versus what can be counted:the complex interplay of market orientation and marketing performance measurement

Market orientation (MO) and marketing performance measurement (MPM) are two of the most widespread strategic marketing concepts among practitioners. However, some have questioned the benefits of extensive investments in MO and MPM. More importantly, little is known about which combinations of MO and MPM are optimal in ensuring high business performance. To address this research gap, the authors analyze a unique data set of 628 firms with a novel method of configurational analysis: fuzzy-set qualitative comparative analysis. In line with prior research, the authors find that MO is an important determinant of business performance. However, to reap its benefits, managers need to complement it with appropriate MPM, the level and focus of which vary across firms. For example, whereas large firms and market leaders generally benefit from comprehensive MPM, small firms may benefit from measuring marketing performance only selectively or by focusing on particular dimensions of marketing performance. The study also finds that many of the highest-performing firms do not follow any of the particular best practices identified.

Espaço de todos ou de ninguém: análise morfológica de transformações espaciais dos Conjuntos Residenciais Parque Serrambi em Natal/ RN

This work analyses the effects of form over the emergence of new patterns of use and occupation in public spaces of housing estates designed in the 1980s and 1990s in Natal’s municipality (Brazil). We start from the premise that form acts on social process (HILLIER; HANSON, 1984), and verify how much the original spatial configuration of Parque Serrambi housing states contributed to the creation of new spatial patterns following the interventions of the people living there. The Serrambi states were built in Natal’s south based on an urbanization model following modernist’s principals and aimed to supply demands for popular dwellings. They were one of the last estates financed by the former National Dwelling Bank (BNH) and supervised by the Dwelling Cooperatives Orientation Institute (INOCOOP), materialized a spatial form different from the highrise dwelling experiences from the same period. The results were obtained through configurational analysis based on Space Syntax conceptual and methodological framework, in which space and society are viewed as interrelated. The analyses was based on represanting and quantifying spatial properties and identificatying social patterns related to the interventions. We identified that the original spatial configurations, associated to subtle changes in the states social patterns, analysed independently of non-morphological categories, gave way to the occupation patterns verrified in both Serrambi cases.

A configuração urbana do território do Vale do Neiva, Viana do Castelo

A dissertação tem como foco a pesquisa sobre a configuração urbana do estudo de caso, a Unidade Territorial de Vale do Neiva em Viana do Castelo. É um território que contem potencial locativo capaz de promover internamente a fixação industrial, as actividades terciárias e a capacidade em fixar e atrair população. Por outro lado, apresenta dinâmicas e valências económicas em contexto concelhio e regional. A análise configuracional abordada na investigação, através do recurso a técnicas e métodos da Sintaxe Espacial, apura características morfológicas do território permitindo a melhor compreensão do funcionamento e da relação entre forma urbana e relações sociais que a envolvem. Foi abordada a dimensão económica-espacial, nomeadamente, no que diz respeito aos seus componentes e interdependências, visando compreender como se processa a apropriação espacial na malha urbana. A correlação desta abordagem com a metodologia da Sintaxe Espacial possibilitou aumentar conhecimento sobre níveis de acessibilidade das actividade presentes no território. Permitem, adicionalmente, a obtenção de análises mais estruturadas que poderão apoiar decisões tecnicamente mais robustas. Por fim, foi diagnosticado o impacto de algumas acções previstas no Plano Director Municipal de Viana do Castelo, designadamente, as que recaem sobre a rede viária da Unidade Territorial do Vale do Neiva. A análise assentou na simulação e previsão dos efeitos das transformações sobre a configuração urbana. Informa, fundamentadamente, sobre estratégias de planeamento e gestão urbana previstas.

Identifying the configurational paths to innovation in SMEs:a fuzzy-set qualitative comparative analysis

Using fuzzy-set qualitative comparative analysis (fsQCA), this study investigates the conditions leading to a higher level of innovation. More specifically, the study explores the impact of inter-organisational knowledge transfer networks and organisations' internal capabilities on different types of innovation in Small to Medium size Enterprises (SMEs) in the high-tech sector. A survey instrument was used to collect data from a sample of UK SMEs. The findings show that although individual factors are important, there is no need for a company to perform well in all the areas. The fsQCA, which enables the examination of the impacts of different combinations of factors, reveals that there are a number of paths to achieve better incremental and radical innovation performance. Companies need to choose the one that is closest to their abilities and fits best with their resources.

Conformational restrictions of peptides via backbone modification: Solution and crystal-state analysis of Boc-L-Pro-DZPhe-Gly-NH2

An N-alpha-protected model tripeptide amide containing, in the central position, an alpha,beta-dehydrophenylalanine (Z-configurational isomer), Boc-L-Pro-DELTA-Z-Phe-Gly-NH2 (Boc, tert-butyloxycarbonyl), has been synthesized by solution methods and fully characterized. IR absorption and H-1 NMR studies provided evidence for the occurrence of a significant population of a conformer containing two consecutive, intramolecularly H-bonded (type II-III') beta-bends in solution. However, an X-ray diffraction analysis clearly indicates that only the type-II beta-bend structure survives in the crystal state.

Facile protocols for the configurational assignment of primary amines and hydroxy acids by NMR

Three-component chiral derivatization protocols are proposed for the assignment of the absolute configurations of chiral primary amines and chiral hydroxy acids using H-1-NMR. The protocols involve simple mixing of the ternary components in CDCl3, followed by stirring for 15 min. The spectra can be recorded directly, without invoking any separation method, unlike many other chiral derivatizing agents. The protocols permit the analysis in less than 15 min, making them convenient and effective for the assignment of the absolute configurations of primary amines and hydroxy acids.

Configurational preferences of two 1,2-diamine adducts of bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)

The preparation, the IR and ligand field spectra and the structures of the mixed-ligand addition compounds [(N,N-dimethyl-1,2-diaminoethane)bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)], [Co(thtf)2me2en], and [(N,N,N′,N′-tetramethyl-1,2-diaminoethane)bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)], [Co(thtf)2me4en], are reported. The structures were determined by single crystal X-ray diffraction analysis (monoclinic, space group P21/c, Z=4 with a=10.708(6), b=19.531(6), c=13.352(6) Å, β=111.64(10)°, R1=0.0642 and wR2=0.1719 for [Co(thtf)2(me2en)] and a=12.033(6), b=15.565(6), c=15.339(6) Å, β=92.57(6)°, R1=0.0612 and wR2=0.1504 for [Co(thtf)2me4en]). The structures are distorted octahedral and the shortest cobalt–cobalt separation distances are 5.388(2) Å in [Co(thtf)2me2en] and 8.675(3) Å in [Co(thtf)2me4en]. In both compounds the diamine molecules attain the gauche conformation. The U(Z,Z) conformation of the β-dione leads to a semi-chair conformation of the β-dionato chelate rings. The relative orientation of the groups attached to the β-dionato moiety depends on the extent of stereoelectronic effects the N-substitution of the diamine entails. In [Co(thtf)2me2en] the intraligand distance separating the trifluoromethyl carbon atoms is 5.281(18) Å while in [Co(thtf)2me2en] it increases to 8.338(9) Å. The cobalt–cobalt separation distance, the orientation of the chelate rings and the extent of N-substitution seem to affect hydrogen bonding. While in [Co(thtf)2me2en] inter- and intraligand hydrogen bonding is implicated, it is totally absent in [Co(thtf)2me4en].